WO2016181407A1 - Additive composition for mixed metal oxide catalysts and its use in hydrocarbon conversion processes - Google Patents
Additive composition for mixed metal oxide catalysts and its use in hydrocarbon conversion processes Download PDFInfo
- Publication number
- WO2016181407A1 WO2016181407A1 PCT/IN2016/000061 IN2016000061W WO2016181407A1 WO 2016181407 A1 WO2016181407 A1 WO 2016181407A1 IN 2016000061 W IN2016000061 W IN 2016000061W WO 2016181407 A1 WO2016181407 A1 WO 2016181407A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- metal oxide
- additive composition
- mixed metal
- catalyst
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- 239000000203 mixture Substances 0.000 title claims abstract description 104
- 239000000654 additive Substances 0.000 title claims abstract description 73
- 230000000996 additive effect Effects 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 55
- 229910003455 mixed metal oxide Inorganic materials 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 21
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000000737 periodic effect Effects 0.000 claims abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 150000002602 lanthanoids Chemical group 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000006317 isomerization reaction Methods 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 19
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 230000029936 alkylation Effects 0.000 claims description 7
- 238000005804 alkylation reaction Methods 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 229920001992 poloxamer 407 Polymers 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000011369 resultant mixture Substances 0.000 claims description 4
- 238000001350 scanning transmission electron microscopy Methods 0.000 claims description 4
- 238000010555 transalkylation reaction Methods 0.000 claims description 4
- 238000004627 transmission electron microscopy Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000010436 fluorite Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229920004890 Triton X-100 Polymers 0.000 claims description 2
- 239000013504 Triton X-100 Substances 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 230000020335 dealkylation Effects 0.000 claims description 2
- 238000006900 dealkylation reaction Methods 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 125000001741 organic sulfur group Chemical group 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 3
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- -1 Platinum group metals Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- B01J35/633—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- the present invention relates to an additive composition which when added to mixed metal oxide catalysts increases the performance of the mixed metal oxide catalyst and requires lower usage of group VIII metals viz. Platinum group metals which are commonly used for increasing the life of the catalyst.
- the present invention also relates to a process for preparing the afore-mentioned additive composition.
- the present invention further relates to hydrocarbon conversion processes carried out using the mixed metal oxide catalysts which comprises the additive composition.
- Chlorine doped alumina catalysts and Zeolites have been popular catalysts for several hydrocarbon reactions used in petroleum processes, specifically isomerization reactions. While CI7AI2O3 catalysts exhibit excellent activity and selectivity towards hydrocarbon reactions, they are highly sensitive to feed contaminants such as water (H 2 0), organic sulfur and organic nitrogen and hence require highly capital intensive feed pretreatment procedures for their usage. They further produce harmful hydrochloric acid downstream which needs to be treated adding to the process costs. Zeolites on the other hand do not require pre- or post-treatment but are significantly lower in terms of their activity. A tradeoff thus exists between the two catalysts and refiners are often left to choose between both the popular options either trading off in terms of performance or costs.
- An optimal hydrocarbon conversion catalyst specifically for isomerization reactions possesses the following traits. It is importantto satisfy all three criteria described below ⁇ for superior performance. a. Low temperature operation: Isomerization reaction is an equilibrium reaction and the forward reaction which is desired for maximum product yield is facilitated at low temperatures ( ⁇ 135°C).
- the former attribute shields the catalyst towards feed contaminants such as sulfur and nitrogen
- the latter attribute facilitates efficient use of hydrogen on the surface thus minimizing its usage in the feed and also suppressing coke formation on the surface.
- the catalyst is further loaded with Nickel, Titanium, Germanium, Manganese, Cobalt, Bismuth, Iron, Vanadium, Cobalt, Zirconium and mixtures thereof.
- the catalyst as disclosed in the aforementioned patent is used for the isomerization reaction; however, the catalyst demonstrates very poor stability.
- the concentration of 2, 2- Dimethyl butane (2, 2-DMB) a key performance metric in the product stream decreases after 200 hours operation from 28% to 14%.
- This catalyst formulation also requires higher quantities of Platinum group (Group VIII) metals to maintain performance over extended periods of operation.
- US Patent No. 3032599 disclosed one of the first usages of sulfated zirconia to isomerization and alkylation of hydrocarbons.
- the catalysts showed high initial activity but not prolonged performance due to low surface area.
- these powdery catalysts are for the most part unusable in industrial reactors due to pressure drop implications.
- US Patent No. 31321 10 discloses the use of sulfated zirconia catalyst, pure or preferably combined with alumina.
- the catalysts obtained herein are indeed excellent in terms of initial activity but do not show prolonged performance. Further, they need very high operating temperatures of over 370°C which results in poor product yields. Also, these catalysts undergo accelerated deactivation due to coke deposition on the surface during operation.
- US Patent No. 6448198 discloses the synthesis of high surface area and mesopore zirconia structures which when sulfated gives superior performance with isomerization reactions.
- these catalysts suffer with significant inhibition from feed contaminants such as organic sulfur and nitrogen.
- Their performance in terms of peak yield of the desired product 2, 2-DMB degrades from 27% to 12% in the presence of 5ppm of either sulfur or nitrogen in the feed stream.
- European patent application No. 1002579 discloses a layered catalyst having zirconium core component followed by Mn, Fe or Ni shell and a top layer consisting of noble metals.
- the catalyst was used for the isomerization reaction. However, the catalyst shows degradation in overall performance after 200 hours of operation. The concentration of 2, 2-DMB, a key performance product decreases from 28% to 20%.
- Another Russian patent document 2171713 discloses a process for the preparation of a catalyst with 0.2 to 1 % platinum or Palladium, 0.05 to 2.5 % chlorine and 0.5 to 10 % sulfate which are deposited on a mixture of aluminum and zirconium oxide.
- the major disadvantage of this catalyst is low stability for isomerization reaction and higher use of reactant hydrogen. A hydrogen to oil ratio of 5 to 10 is required to maintain stability of such a catalyst over extended operating periods.
- US Patent No. 7015175 discloses a method for the synthesis of sulfated zirconium catalyst doped with high concentration (of at least 3 %) of Lanthanide series elements.
- the performance of such a catalyst degrades substantially in the presence of organic sulfur or nitrogen based contaminants which are typically seen in the petroleum feed stream.
- the yield of 2, 2-DMB reduces from 28% to 14% with 5ppm of sulfur in the feed stream.
- the operating temperature as described in the patent is substantially high ( ⁇ 170°C) for optimal operation. Isomerization is an equilibrium reaction and high conversion is facilitated at low temperatures ( ⁇ 130°C).
- the present invention provides a highly efficient additive composition which can be directly added to the mixed metal oxide catalysts.
- the additive composition increases the performance of the catalyst, favors low temperature operations, increases tolerance to feed contaminants and decelerates the catalyst growth for high product selectivity.
- the present invention provides an additive composition having the general formula:
- A is one or more metal elements selected from the group consisting of
- B, C is one or more metal elements selected from the lanthanide group series of the periodic table or Yttrium;
- D is one or more metal elements selected from the group consisting of Manganese, Cobalt, Copper, Nickel or Ruthenium;
- x is a number defined by 0.5 ⁇ x ⁇ 4
- z is a number defined by 2 ⁇ z ⁇ 6
- m is a number which renders the catalyst substantially neutral.
- the present invention provides a process for preparing the aforementioned additive composition comprising:
- step (a) adding a precipitating agent to the resultant mixture of step (a);
- step (b) adjusting the pH of the solution of step (b) to about 9 - 12;
- step (c) filtering and washing the resulting precipitant of step (c);
- step ' (d) calcining the precipitant of step ' (d) at 300°C to 600°C for 1 hour to 6 hours to obtain the additive composition.
- Another aspect of the present invention is to provide mixed metal oxide catalysts comprising the afore-mentioned additive composition.
- Yet another aspect of the present is to provide processes for converting hydrocarbons by contacting a feed with the afore-mentioned mixed metal oxide catalyst which comprises the additive composition.
- Figure 1 X-ray diffraction pattern of additive composition for catalyst Zl of the present invention which shows the onset of the crystal formation.
- Figure 2 X-ray diffraction pattern of additive composition for catalyst Z2 of the present invention which shows the onset of the crystal formation.
- Figure 3 X-ray diffraction pattern of additive composition for catalyst Z3 of the present invention which shows the onset of the crystal formation.
- the present invention provides an additive composition comprising mixed metal oxide having the general formula:
- A is one or more metal elements selected from the group consisting of Group IIA of the periodic table;
- B, C is one or more metal elements selected from the lanthanide group series of the periodic table or Yttrium;
- D is one or more metal elements selected from the group consisting of . Manganese, Cobalt, Copper, Nickel or Ruthenium;
- x is a number defined by 0.5 ⁇ x ⁇ 4
- z is a number defined by 2 ⁇ z ⁇ 6
- m is a number which renders the catalyst substantially neutral.
- Element A is selected from the group consisting of Strontium, Magnesium, Barium or mixtures thereof.
- Elements B and C are selected from the group consisting of Cerium, Samarium, Ytterbium, Lanthanum, Neodymium, Yttrium or mixtures thereof.
- element A is Strontium
- B is Cerium or Yttrium
- G is Samarium or Ytterbium
- D is Manganese or Ruthenium.
- the mole percent of element A is in the range of 0.1 ⁇ A ⁇ 0.25; mole percent of elements B, C are in the range of 0.05 ⁇ B, C ⁇ 0.2; mole percent of element D is in the range of 0.1 ⁇ D ⁇ 0.35; and the valence charge of oxygen is such that the overall charge of the molecule is neutral.
- the additive composition has the general formula:
- B, C is one or more metal elements selected from the lanthanide group series of the periodic table or Yttrium;
- D is one or more metal elements selected from the group consisting of Manganese, Cobalt, Copper, Nickel or Ruthenium;
- x is a number defined by 0.5 ⁇ x ⁇ 4
- z is a number defined by 2 ⁇ z ⁇ 6
- m is a number which renders the catalyst substantially neutral.
- the present invention provides a process for preparing the aforementioned additive composition comprising:
- step (a) adding a precipitating agent to the resultant mixture of step (a);
- step (b) adjusting the pH of the solution of step (b) to about 9 - 12;
- step (c) filtering and washing the resulting precipitant of step (c);
- step (d) e. calcining the precipitant of step (d) at 300°C to 600°C for 1 hour to 6 hours to obtain the additive composition.
- the additive composition may be prepared by co-precipitation method or sequential precipitation method wherein suitable amounts of metal salt precursors such as but not limited to nitrate salts or acetate salts or chloride salts or sulfate salts are dissolved in water.
- the resultant mixture of metal cations is then precipitated using a precipitating agent.
- the precipitating agent may also act as a surfactant to create the desired crystal structure.
- Suitable precipitating agent may be selected from the group consisting of sodium hydroxide, sodium carbonate, oxalic acid, sodium oxalate, ammonium oxalate or mixtures thereof and may be added in an amount so as to obtain a final pH value of at least 9 or above.
- step (b) The pH of solution of step (b) is adjusted between 9 - 12 using tetramethylammonium hydroxide (TMAOH). Additional TMAOH may be added to reestablish the pH of the solution.
- TMAOH tetramethylammonium hydroxide
- the resultant metal precipitant is filtered and washed using deionized water for three to four times. Finally, the metal precipitant is dried, processed and calcined at 500°C for 4 hours.
- the afore-mentioned process may optionally comprise adding an oxidizing agent or a surfactant to the mixture of step (a).
- Said oxidizing agent may be selected from the group consisting of hydrogen peroxide, chlorate, perchlorate, hypochlorite, nitric acid, sulfuric acid, potassium permanganate or mixtures thereof and may be added in an amount of 100% in excess of the moles of element D used in the additive composition.
- Said surfactant may be selected from the group consisting of polyvinyl alcohol (PVA), Triton X-100, Pluronic F127, Polyethylene glycol (PEG), sodium salt of polyacrylic acid (Na-PAA) or mixtures thereof and may be added in an amount of 50% in excess of the moles of element A used in the additive composition.
- the additive composition may be partially calcined to start the formation of the desired crystals which when mixed with the mixed metal oxide catalyst such as the sulfated alumina zirconia catalyst will allow optimal crystal formation during final calcination procedure.
- the additive may not be fully calcined wherein X-ray diffraction does not reveal fully crystalline structures but only reveals partially crystalline and partially amorphous phases.
- the additive composition may be prepared using the citric acid method.
- Said method includes dissolving suitable amounts of the different metal salts in water with 10% excess of molar amounts of citric acid.
- all or a portion of the citric acid may be substituted with Ethylene diamine tetraacetic acid (EDTA) or a mixture of Polyvinyl alcohol (PVA) and sucrose.
- EDTA Ethylene diamine tetraacetic acid
- PVA Polyvinyl alcohol
- sucrose sucrose
- the mixture is stirred and heated until a viscous gel forms.
- the viscous gel is dried, processed, and calcined at 500°C for 4 hours.
- the present invention provides a mixed metal oxide catalyst comprising the afore-mentioned additive composition.
- Said mixed metal oxide catalyst is selected from the group consisting of Group III and Group IV of the periodic table.
- the mixed metal oxide catalyst is selected from the group consisting of a sulfated or a tungsated metal oxide of Zirconium or Aluminum or mixtures thereof.
- Said mixed metal oxide catalyst may optionally consist of a hydrogenating metal selected from the group consisting of Manganese, Iron, Gallium, Copper, Cobalt or mixtures thereof.
- the afore-mentioned mixed metal oxide catalyst may further comprise a Group VIII metal selected from the group consisting of Platinum, Palladium, Rhenium, Rhodium, Iridium, Ruthenium, Gold or mixtures thereof. In an embodiment of the present invention, about 0.1% to 5% of Group VIII metal may be present in the mixed metal oxide catalyst. Said Group VIII metal in small amounts may be added to the final mixed metal oxide catalyst by usual impregnation techniques known to those skilled in the art.
- One of the specific advantages of the additive composition of the present invention is to provide the optimal charge density on the surface catalyst to enable further ion doping. For example, most hydrocarbon processes require small quantities of Platinum group metals (PGM) to be further added to the final catalyst recipe to enhance long term performance.
- PGM Platinum group metals
- PGM is typically added to the catalyst by dry impregnation method which while cheaper does not give optimal control on the location of PGM on the surface of the catalyst leading to non-optimal performance.
- the additive composition described in the present invention when added to the catalyst will provide the interionic repulsive forces thus increasing the dispersion (or surface area) of the PGM metals on the surface, thus dramatically improving the PGM surface area. Larger PGM surface area results directly in increasing catalyst longevity and reactivity. Further, the additive also increases the metal support interactive forces thus decreasing the stronger binding forces of the PGM metals towards undesirable feed contaminants such as sulfur and nitrogen.
- the additive composition may be directly added to sulfated zirconia catalysts as described in the open literatures titled 1) "Effect of isopropanol aging of Zr(OH) 4 on n-hexane isomerization over Pt-S0 4 2" /Al 2 0 3 -Zr0 2 , Catalysis Today, Oct 2009, 148 (1 -2), p 70-74, 2) "Catalytic performance of Re/Ga 2 0 3 /W0 3 /Zr0 2 catalyst for n-Hexane isomerization", Chi.J. of. Catal. Sept 2009, 30(9), p 859-863).
- the additive composition can be directly added to mixed metal oxide catalysts in varying ratios to the sulfated zirconia catalyst such as Pt-S0 4 7A1 2 0 3 /Zr0 2 catalysts to obtain the desired results.
- the additive composition is added to the mixed metal oxide catalyst prior to calcination and about 0.5 to 25 weight percent of the additive composition is added to the mixed metal oxide catalyst.
- the sulfated mixture of A1 2 0 3 and Zr0 2 in their hydroxide form should be intimately mixed with the additive composition in ratios of 2 to 25% so as to obtain maximum benefit.
- the additive composition of the present invention may be synthesized separately from the mixed metal oxide catalyst (such as sulfated alumina zirconia catalyst).
- the synthesis of the sulfated alumina zirconia catalyst along with some transition metal additive may be done through the processes as described in the open literature titled 1 ) "Effect of isopropanol aging of Zr(OH) on n-hexane isomerization over Pt-SC 2' /Al 2 0 3 -Zr0 2 , Catalysis Today, Oct 2009, 148 (1 -2), p 70-74, and 2) "Catalytic performance of Re/Ga 2 0 3 /W0 3 /Zr0 2 catalyst for n-Hexane isomerization", Chi.J. of. Catal., Sept 2009, 30(9), p 859-863.
- High surface area Zr(OH) 4 and pseudo boehmite may be mulled together and extruded using sulfate ion additive such as sulfuric acid or ammonium sulfate followed by drying at 120 ° C for several hours.
- sulfate ion additive such as sulfuric acid or ammonium sulfate followed by drying at 120 ° C for several hours.
- a transition metal ion may be added to increase the hydrogenation ability of the catalyst.
- the additive composition synthesized will have at least two phases namely a spinel phase and a mullite phase or a fluorite phase oxide when characterized with Transmission Electron Microscopy (TEM) or Scanning Transmission Electron Microscopy (STEM)/ Energy-disperisve X-ray Analyser (EDX) techniques.
- the spinel phase and/or the fluorite phase and/or the mullite phase can include one or more metals.
- the mixed phase catalyst additive composition may include a composite having two or more constituent materials with different physical or chemical properties which remain separate and distinct at the macroscopic or microscopic scale within the finished structure. For example, two particles with different compositions remain separate in TEM ("Transmission Electron Microscopy") while they do have common interface.
- the present invention provides a process for converting hydrocarbons by contacting a feed with the mixed metal oxide catalyst having the additive composition.
- Said hydrocarbon conversion process may be selected from the group consisting of cracking, hydrocracking, aromatic alkylation, isoparaffin alkylation, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation or dealkylation, preferably, isomerization, alkylation or transalkylation.
- the additive composition described in the present invention enhances the performance of mixed metal oxide catalysts towards hydrocarbon processing reactions such as but not limited to isomerization.
- the additive composition of the present invention specifically mention of
- Catalyst A was prepared using the well-established sulfated alumina zirconia synthesis route as known to those skilled in the art as shown in US Pat No. 6,448,198 B l .
- the corresponding references for the catalyst design have been provided for reference. Briefly, high surface area Zirconium hydroxide (Zr(OH) 4 ) and pseudo-boehmite were co-mulled together to form an intimate mixture. They were then extruded into 1mm diameter and 2mm length extrudes. The extrudes were then exposed to 1 M sulfuric acid (15 ml/gm of extrudes) and subsequently vacuum filtered to remove the excess sulfate ions.
- Zr(OH) 4 high surface area Zirconium hydroxide
- pseudo-boehmite pseudo-boehmite were co-mulled together to form an intimate mixture. They were then extruded into 1mm diameter and 2mm length extrudes. The extrudes were then exposed to 1 M sulfuric acid (15
- the extrudes were then calcined at 600°C for 3 hours to form crystalline sulfated alumina zirconia catalyst.
- the catalyst had 0.24 ml/g pore volume at the end of the calcination.
- Platinum with 0.3 wt% was then incoiporated into the catalyst by wet impregnation technique as known to those skilled in the art. This catalyst was designated catalyst A.
- Catalyst B was prepared using the popular metal doped sulfated zirconia catalyst synthesis route as known to those skilled in the art and also described in the patent, EP0532153B1. Briefly, high surface area zirconium hydroxide was prepared by rapidly mixing zirconium carbonate and ammonia solutions. After washing and sieving to desired size, Iron (Fe) and Manganese (Mn) nitrate solutions were added to the support material via incipient wetness impregnation method. The catalyst was subsequently dried and calcined at 725°C for one hour. 0.3% Platinum was incorporated into the catalyst via incipient wetness impregnation method. The testing procedure described in example 1 was used to evaluate catalyst B's performance. The results of which are detailed in Table 2.
- Base catalyst was synthesized using the method described in the open literature (reference provided in the previous sections). Briefly, high surface zirconium hydroxide and pseudo boehmite were co-mulled together and impregnated with IN H 2 S0 by using 15ml/gm- of the support material. Excess acid was drained and the sulfated support was dried at 120°C for several hours. Gallium was then introduced into the support by adding its corresponding nitrate salt to achieve 3% loading by incipient wetness technique. The mixture was then dried and is labeled Catalyst Z. Additive Composition 1 - Catalyst Zl
- Additive for catalyst Zl was first prepared by mixing nitrate salts of Strontium, Cerium, Samarium and Manganese. 25.5 gms of Mn(N0 3 ) 2 50% solution, 5 gms of Sr(N0 3 ) 2 , 9.3 gms of Ce(N0 3 ) 3 .6H 2 0 1.1 gms of Sm(N0 3 ) 3 .6H 2 0 were mixed together in desired amount of water. 13.4 gms of 35% H 2 0 2 was added to the mixture while stirring. 2.4 gms of Oxalic acid was then added to the mixture.
- the additive thus produced is added to catalyst Z shown in example 1 and extruded into lmm diameter and 2mm length extrudes.
- the final catalyst formulation was calcined at 700°C for 3 hours.
- 0.3 wt% Platinum was added to the calcined extrudes by incipient wetness impregnation method.
- the catalyst is labeled Zl and the isomerization test results with the feed shown in comparative example 1 are shown in Table 2.
- Additive for catalyst Z2 was first prepared by mixing nitrate salts of Strontium, Cerium, Ytterbium and Manganese. 25.5 gms of Mn(N0 3 ) 2 50% solution, 5 gms of Sr(N0 3 ) 2 , 9.3 gms of Ce(N0 3 ) 3 .6H 2 0 1.1 gms of Yb(N0 3 ) 3 .63 ⁇ 40 were mixed together in desired amount of water. 13.4 gms of 35% H 2 0 2 was added to the mixture while stirring. 2.4 gms of Oxalic acid was then added to the mixture.
- the additive thus produced is added to catalyst Z shown in example 1 and extruded into 1mm diameter and 2mm length extrudes.
- the final catalyst formulation was calcined at 700°C for 3 hours.
- 0.3 wt% Platinum was added to the calcined extrudes by incipient wetness impregnation method.
- the catalyst is labeled Z2 and the isomerization test results with the feed shown in comparative example 1 is shown in Table 2.
- Additive for catalyst Z3 was first prepared by mixing nitrate salts of Strontium, Cerium, Ytterbium and Ruthenium. 17 gms of Ru(N0 3 ) 2 , 5 gms of Sr(N0 3 )2, 9.3 gms of Ce(N0 3 ) 3 .6H 2 0 1.1 gms of Yb(N0 3 ) 3 .6H 2 0 were mixed together in desired amount of water. 13.4 gms of 35% H 2 0 2 was added to the mixture while stirring. 2.4 gms of Oxalic acid was then added to the mixture.
- the additive thus produced is added to catalyst Z shown in example 1 and extruded into lmm diameter and 2mm length extrudes.
- the final catalyst formulation was calcined at 700°C for 3 hours.
- 0.3 wt% Platinum was added to the calcined extrudes by incipient wetness impregnation method.
- the catalyst is labeled Z2 and the isomerization test result with the feed shown in comparative example 1 is shown in
- catalysts prepared with the invention described herein namely catalysts Zl , Z2 and Z3 exhibit excellent performance characteristics in terms of product conversion, low temperature operation and high tolerance to feed contaminants.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides an additive composition having the general formula: AxByC(1-y)DzOm wherein: A is one or more metal elements selected from the group consisting of Group IIA of the periodic table; B, C is one or more metal elements selected from the lanthanide group, series of the periodic table or Yttrium; D is one or more metal elements selected from the group consisting of Manganese, Cobalt, Copper, Nickel or Ruthenium; x is a number defined by 0.5 < x < 4; y is a number defined by 0<=y<=l; z is a number defined by 2 < z < 6; m is a number which renders the catalyst substantially neutral. The present invention also provides a process for preparing the afore-mentioned additive composition. The present invention further provides mixed metal oxide catalysts comprising additive composition and its use in hydrocarbon conversion processes.
Description
ADDITIVE COMPOSITION FOR MIXED METAL OXIDE CATALYSTS AND ITS USE IN HYDROCARBON CONVERSION PROCESSES
The present application claims priority of Indian patent application no. 1840/MUM/2015, "ADDITIVE COMPOSITION FOR MIXED METAL OXIDE CATALYSTS AND ITS USE IN HYDROCARBON CONVERSION PROCESSES", filed on 8 May 2015, the whole content of which is hereby incorporated for reference. FIELD OF THE INVENTION
The present invention relates to an additive composition which when added to mixed metal oxide catalysts increases the performance of the mixed metal oxide catalyst and requires lower usage of group VIII metals viz. Platinum group metals which are commonly used for increasing the life of the catalyst. The present invention also relates to a process for preparing the afore-mentioned additive composition. The present invention further relates to hydrocarbon conversion processes carried out using the mixed metal oxide catalysts which comprises the additive composition.
BACKGROUND OF THE INVENTION
Chlorine doped alumina catalysts and Zeolites have been popular catalysts for several hydrocarbon reactions used in petroleum processes, specifically isomerization reactions. While CI7AI2O3 catalysts exhibit excellent activity and selectivity towards hydrocarbon reactions, they are highly sensitive to feed contaminants such as water (H20), organic sulfur and organic nitrogen and hence require highly capital intensive feed pretreatment procedures for their usage. They further produce harmful hydrochloric acid downstream which needs to be treated adding to the process costs. Zeolites on the other hand do not require pre- or post-treatment but are significantly lower in terms of their activity. A tradeoff thus exists between the two catalysts and refiners are often left to choose between both the popular options either trading off in terms of performance or costs.
An optimal hydrocarbon conversion catalyst specifically for isomerization reactions possesses the following traits. It is importantto satisfy all three criteria described below^ for superior performance.
a. Low temperature operation: Isomerization reaction is an equilibrium reaction and the forward reaction which is desired for maximum product yield is facilitated at low temperatures (<135°C).
b. High tolerance to feed contaminants and efficient hydrogen splitting: Both these attributes typically are obtained from the metallic sites on the doped support.
While the former attribute shields the catalyst towards feed contaminants such as sulfur and nitrogen, the latter attribute facilitates efficient use of hydrogen on the surface thus minimizing its usage in the feed and also suppressing coke formation on the surface.
c. Optimal pore structure of the support: This is required to maximize the selectivity of the desired products,
Hino et al. (1980) in their seminal paper - "Synthesis of Solid superacid catalyst with acid strength of HO < -16.04", J. C.S. Chem. Comm., 851 - 852, 573, 1980 explained the usage of anion modified Group III and Group IV oxides such as WC ZrC^ and SO4 " /Zr02 catalysts as strong acids which exhibit promising performance in hydrocarbon conversion processes such as isomerization. While these catalysts show moderate performance tradeoff in comparison to the CI7AI2O3 catalysts, they do not need the feed pretreatment and thus the tradeoff between costs and performance is to a lower extent for the refiner in comparison to the Zeolite catalysts. While several patents and papers have been published improving the design of the originally proposed catalyst by Hino et al. prolonged catalyst stability was not achieved which is essential for commercial petroleum applications. This prior art describes the usage of sulfated zirconia catalysts which at most satisfy two of the above attributes thus leading to non- optimal performance in hydrocarbon conversion processes such as isomerization.
More recently substantial research has been conducted to improve the stability and longevity of these anion modified acid catalysts and several patents have been filed exhibiting their advanced stability for petroleum processes such as isomerization, alkylation and transalkylation - US Patent No. 6107235 and 6080904 etc.
Further, the use of several dopant systems is reported to increase the stability of these catalyst compositions, for example, Russian patent document 2191627 discloses a method for the synthesis of sulfated zirconia catalyst loaded with noble metals such as platinum, palladium, ruthenium, osmium, iridium and the like on an zirconia support containing up to 20 % of active components of silicon, titanium oxide, magnesium and alumina. The catalyst is further loaded with Nickel, Titanium, Germanium, Manganese, Cobalt, Bismuth, Iron, Vanadium, Cobalt, Zirconium and mixtures thereof. The catalyst as disclosed in the aforementioned patent is used for the isomerization reaction; however, the catalyst demonstrates very poor stability. The concentration of 2, 2- Dimethyl butane (2, 2-DMB) a key performance metric in the product stream decreases after 200 hours operation from 28% to 14%. This catalyst formulation also requires higher quantities of Platinum group (Group VIII) metals to maintain performance over extended periods of operation. US Patent No. 3032599 disclosed one of the first usages of sulfated zirconia to isomerization and alkylation of hydrocarbons. The catalysts showed high initial activity but not prolonged performance due to low surface area. Furthermore, these powdery catalysts are for the most part unusable in industrial reactors due to pressure drop implications.
US Patent No. 31321 10 discloses the use of sulfated zirconia catalyst, pure or preferably combined with alumina. The catalysts obtained herein are indeed excellent in terms of initial activity but do not show prolonged performance. Further, they need very high operating temperatures of over 370°C which results in poor product yields. Also, these catalysts undergo accelerated deactivation due to coke deposition on the surface during operation.
US Patent No. 6448198 discloses the synthesis of high surface area and mesopore zirconia structures which when sulfated gives superior performance with isomerization reactions. However, these catalysts suffer with significant inhibition from feed contaminants such as organic sulfur and nitrogen. Their performance in terms of peak
yield of the desired product 2, 2-DMB degrades from 27% to 12% in the presence of 5ppm of either sulfur or nitrogen in the feed stream.
European patent application No. 1002579 discloses a layered catalyst having zirconium core component followed by Mn, Fe or Ni shell and a top layer consisting of noble metals. The catalyst was used for the isomerization reaction. However, the catalyst shows degradation in overall performance after 200 hours of operation. The concentration of 2, 2-DMB, a key performance product decreases from 28% to 20%. Another Russian patent document 2171713 discloses a process for the preparation of a catalyst with 0.2 to 1 % platinum or Palladium, 0.05 to 2.5 % chlorine and 0.5 to 10 % sulfate which are deposited on a mixture of aluminum and zirconium oxide. The major disadvantage of this catalyst is low stability for isomerization reaction and higher use of reactant hydrogen. A hydrogen to oil ratio of 5 to 10 is required to maintain stability of such a catalyst over extended operating periods.
US Patent No. 7015175 discloses a method for the synthesis of sulfated zirconium catalyst doped with high concentration (of at least 3 %) of Lanthanide series elements. The performance of such a catalyst degrades substantially in the presence of organic sulfur or nitrogen based contaminants which are typically seen in the petroleum feed stream. The yield of 2, 2-DMB reduces from 28% to 14% with 5ppm of sulfur in the feed stream. Also, the operating temperature as described in the patent is substantially high (~ 170°C) for optimal operation. Isomerization is an equilibrium reaction and high conversion is facilitated at low temperatures (~ 130°C).
Thus in order to overcome the limitations of the prior arts described above, the present invention provides a highly efficient additive composition which can be directly added to the mixed metal oxide catalysts. The additive composition increases the performance of the catalyst, favors low temperature operations, increases tolerance to feed contaminants and decelerates the catalyst growth for high product selectivity.
SUMMARY OF THE INVENTION
In one aspect the present invention provides an additive composition having the general formula:
AxByC(,.y)DzOm
wherein:
A is one or more metal elements selected from the group consisting of
Group IIA of the periodic table;
B, C is one or more metal elements selected from the lanthanide group series of the periodic table or Yttrium;
D is one or more metal elements selected from the group consisting of Manganese, Cobalt, Copper, Nickel or Ruthenium;
x is a number defined by 0.5 < x < 4
y is a number defined by 0<=y<=l
z is a number defined by 2 < z < 6
m is a number which renders the catalyst substantially neutral.
In another aspect the present invention provides a process for preparing the aforementioned additive composition comprising:
a. dissolving water soluble salts of A, B, C and D to obtain the general formula of the afore-mentioned additive composition;
b. adding a precipitating agent to the resultant mixture of step (a);
c. adjusting the pH of the solution of step (b) to about 9 - 12;
d. filtering and washing the resulting precipitant of step (c);
e. calcining the precipitant of step '(d) at 300°C to 600°C for 1 hour to 6 hours to obtain the additive composition.
Another aspect of the present invention is to provide mixed metal oxide catalysts comprising the afore-mentioned additive composition.
Yet another aspect of the present is to provide processes for converting hydrocarbons by contacting a feed with the afore-mentioned mixed metal oxide catalyst which comprises the additive composition.
Further scope and applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating embodiments of the invention, are given by way of illustration only, because various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. BRIEF DESCRIPTION OF THE DRAWINGS
The following detailed description of the invention will be better understood when read in conjunction with the appended drawings. For the purpose of assisting in the explanation of the invention, there are shown in the drawings embodiments which are presently preferred and considered illustrative. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown therein.
Figure 1: X-ray diffraction pattern of additive composition for catalyst Zl of the present invention which shows the onset of the crystal formation.
Figure 2: X-ray diffraction pattern of additive composition for catalyst Z2 of the present invention which shows the onset of the crystal formation.
Figure 3: X-ray diffraction pattern of additive composition for catalyst Z3 of the present invention which shows the onset of the crystal formation. DETAILED DESCRIPTION OF THE INVENTION
For the purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantitie ¾of ingredients used in the specification are to be understood as being modified in all instances by the term "about". It is noted that, unless otherwise stated, all percentages
given in this specification and appended claims refer to percentages by weight of the total composition.
Thus, before describing the present invention in detail, it is to be understood that this invention is not limited to particularly exemplified systems or process parameters that may of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments of the invention only, and is not intended to limit the scope of the invention in any manner. The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the case of conflict, the present document, including definitions will control. It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the content clearly dictates otherwise.
The terms "preferred" and "preferably" refer to embodiments of the invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
As used herein, the terms "comprising" "including," "having," "containing," "involving," and the like are to be understood to be open-ended, i.e., to mean including but not limited to.
In one aspect, the present invention provides an additive composition comprising mixed metal oxide having the general formula:
AxByC(,.y)DzOm
wherein:
A is one or more metal elements selected from the group consisting of Group IIA of the periodic table;
B, C is one or more metal elements selected from the lanthanide group series of the periodic table or Yttrium;
D is one or more metal elements selected from the group consisting of . Manganese, Cobalt, Copper, Nickel or Ruthenium;
x is a number defined by 0.5 < x < 4
y is a number defined by 0<=y<=l
z is a number defined by 2 < z < 6
m is a number which renders the catalyst substantially neutral.
Element A is selected from the group consisting of Strontium, Magnesium, Barium or mixtures thereof. Elements B and C are selected from the group consisting of Cerium, Samarium, Ytterbium, Lanthanum, Neodymium, Yttrium or mixtures thereof. Preferably element A is Strontium, B is Cerium or Yttrium, G is Samarium or Ytterbium and D is Manganese or Ruthenium.
In an embodiment of the present invention, the mole percent of element A is in the range of 0.1 < A < 0.25; mole percent of elements B, C are in the range of 0.05 < B, C < 0.2; mole percent of element D is in the range of 0.1 < D < 0.35; and the valence charge of oxygen is such that the overall charge of the molecule is neutral.
In the most preferred embodiment, the additive composition has the general formula:
SrxByC(i-y)DzOm
wherein:
B, C is one or more metal elements selected from the lanthanide group series of the periodic table or Yttrium;
D is one or more metal elements selected from the group consisting of Manganese, Cobalt, Copper, Nickel or Ruthenium;
x is a number defined by 0.5 < x < 4
y is a number defined by 0<-y<=l
z is a number defined by 2 < z < 6
m is a number which renders the catalyst substantially neutral.
In another aspect, the present invention provides a process for preparing the aforementioned additive composition comprising:
a. dissolving water soluble salts of A, B, C and D to obtain the general formula of the afore-mentioned additive composition;
b. adding a precipitating agent to the resultant mixture of step (a);
c. adjusting the pH of the solution of step (b) to about 9 - 12;
d. filtering and washing the resulting precipitant of step (c);
e. calcining the precipitant of step (d) at 300°C to 600°C for 1 hour to 6 hours to obtain the additive composition.
In an embodiment of the present invention, the additive composition may be prepared by co-precipitation method or sequential precipitation method wherein suitable amounts of metal salt precursors such as but not limited to nitrate salts or acetate salts or chloride salts or sulfate salts are dissolved in water. The resultant mixture of metal cations is then precipitated using a precipitating agent. The precipitating agent may also act as a surfactant to create the desired crystal structure. Suitable precipitating agent may be selected from the group consisting of sodium hydroxide, sodium carbonate, oxalic acid, sodium oxalate, ammonium oxalate or mixtures thereof and may be added in an amount so as to obtain a final pH value of at least 9 or above.
The pH of solution of step (b) is adjusted between 9 - 12 using tetramethylammonium hydroxide (TMAOH). Additional TMAOH may be added to reestablish the pH of the
solution. The resultant metal precipitant is filtered and washed using deionized water for three to four times. Finally, the metal precipitant is dried, processed and calcined at 500°C for 4 hours. The afore-mentioned process may optionally comprise adding an oxidizing agent or a surfactant to the mixture of step (a). Said oxidizing agent may be selected from the group consisting of hydrogen peroxide, chlorate, perchlorate, hypochlorite, nitric acid, sulfuric acid, potassium permanganate or mixtures thereof and may be added in an amount of 100% in excess of the moles of element D used in the additive composition. Said surfactant may be selected from the group consisting of polyvinyl alcohol (PVA), Triton X-100, Pluronic F127, Polyethylene glycol (PEG), sodium salt of polyacrylic acid (Na-PAA) or mixtures thereof and may be added in an amount of 50% in excess of the moles of element A used in the additive composition. The additive composition may be partially calcined to start the formation of the desired crystals which when mixed with the mixed metal oxide catalyst such as the sulfated alumina zirconia catalyst will allow optimal crystal formation during final calcination procedure. In another embodiment of the present invention, the additive may not be fully calcined wherein X-ray diffraction does not reveal fully crystalline structures but only reveals partially crystalline and partially amorphous phases.
In another embodiment of the present invention, the additive composition may be prepared using the citric acid method. Said method includes dissolving suitable amounts of the different metal salts in water with 10% excess of molar amounts of citric acid. Optionally, all or a portion of the citric acid may be substituted with Ethylene diamine tetraacetic acid (EDTA) or a mixture of Polyvinyl alcohol (PVA) and sucrose. The mixture is stirred and heated until a viscous gel forms. The viscous gel is dried, processed, and calcined at 500°C for 4 hours. In another aspect, the present invention provides a mixed metal oxide catalyst comprising the afore-mentioned additive composition. Said mixed metal oxide catalyst is selected from the group consisting of Group III and Group IV of the periodic table.
In an embodiment of the present invention, the mixed metal oxide catalyst is selected from the group consisting of a sulfated or a tungsated metal oxide of Zirconium or Aluminum or mixtures thereof. Said mixed metal oxide catalyst may optionally consist of a hydrogenating metal selected from the group consisting of Manganese, Iron, Gallium, Copper, Cobalt or mixtures thereof.
The afore-mentioned mixed metal oxide catalyst may further comprise a Group VIII metal selected from the group consisting of Platinum, Palladium, Rhenium, Rhodium, Iridium, Ruthenium, Gold or mixtures thereof. In an embodiment of the present invention, about 0.1% to 5% of Group VIII metal may be present in the mixed metal oxide catalyst. Said Group VIII metal in small amounts may be added to the final mixed metal oxide catalyst by usual impregnation techniques known to those skilled in the art. One of the specific advantages of the additive composition of the present invention is to provide the optimal charge density on the surface catalyst to enable further ion doping. For example, most hydrocarbon processes require small quantities of Platinum group metals (PGM) to be further added to the final catalyst recipe to enhance long term performance. PGM is typically added to the catalyst by dry impregnation method which while cheaper does not give optimal control on the location of PGM on the surface of the catalyst leading to non-optimal performance. The additive composition described in the present invention when added to the catalyst will provide the interionic repulsive forces thus increasing the dispersion (or surface area) of the PGM metals on the surface, thus dramatically improving the PGM surface area. Larger PGM surface area results directly in increasing catalyst longevity and reactivity. Further, the additive also increases the metal support interactive forces thus decreasing the stronger binding forces of the PGM metals towards undesirable feed contaminants such as sulfur and nitrogen.
In an exemplary embodiment of the present invention, the additive composition may be directly added to sulfated zirconia catalysts as described in the open literatures titled 1) "Effect of isopropanol aging of Zr(OH)4 on n-hexane isomerization over Pt-S04 2" /Al203-Zr02, Catalysis Today, Oct 2009, 148 (1 -2), p 70-74, 2) "Catalytic performance
of Re/Ga203/W03/Zr02 catalyst for n-Hexane isomerization", Chi.J. of. Catal. Sept 2009, 30(9), p 859-863).
The additive composition can be directly added to mixed metal oxide catalysts in varying ratios to the sulfated zirconia catalyst such as Pt-S04 7A1203/Zr02 catalysts to obtain the desired results.
In an embodiment of the present invention, the additive composition is added to the mixed metal oxide catalyst prior to calcination and about 0.5 to 25 weight percent of the additive composition is added to the mixed metal oxide catalyst. In order for the final catalyst to be active, the sulfated mixture of A1203 and Zr02 in their hydroxide form should be intimately mixed with the additive composition in ratios of 2 to 25% so as to obtain maximum benefit. The additive composition of the present invention may be synthesized separately from the mixed metal oxide catalyst (such as sulfated alumina zirconia catalyst). The synthesis of the sulfated alumina zirconia catalyst along with some transition metal additive may be done through the processes as described in the open literature titled 1 ) "Effect of isopropanol aging of Zr(OH) on n-hexane isomerization over Pt-SC 2' /Al203-Zr02, Catalysis Today, Oct 2009, 148 (1 -2), p 70-74, and 2) "Catalytic performance of Re/Ga203/W03/Zr02 catalyst for n-Hexane isomerization", Chi.J. of. Catal., Sept 2009, 30(9), p 859-863. High surface area Zr(OH)4 and pseudo boehmite may be mulled together and extruded using sulfate ion additive such as sulfuric acid or ammonium sulfate followed by drying at 120°C for several hours. In addition a transition metal ion may be added to increase the hydrogenation ability of the catalyst.
In an embodiment of the present invention, the additive composition synthesized will have at least two phases namely a spinel phase and a mullite phase or a fluorite phase oxide when characterized with Transmission Electron Microscopy (TEM) or Scanning Transmission Electron Microscopy (STEM)/ Energy-disperisve X-ray Analyser (EDX) techniques. In another embodiment, the spinel phase and/or the fluorite phase and/or the mullite phase can include one or more metals.
In a further embodiment of the present invention, the mixed phase catalyst additive composition may include a composite having two or more constituent materials with different physical or chemical properties which remain separate and distinct at the macroscopic or microscopic scale within the finished structure. For example, two particles with different compositions remain separate in TEM ("Transmission Electron Microscopy") while they do have common interface.
In a further aspect, the present invention provides a process for converting hydrocarbons by contacting a feed with the mixed metal oxide catalyst having the additive composition.
Said hydrocarbon conversion process may be selected from the group consisting of cracking, hydrocracking, aromatic alkylation, isoparaffin alkylation, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation or dealkylation, preferably, isomerization, alkylation or transalkylation.
The additive composition described in the present invention enhances the performance of mixed metal oxide catalysts towards hydrocarbon processing reactions such as but not limited to isomerization. The additive composition of the present invention specifically
(i) Creates optimal strength acid sites on the surface to facilitate low temperature operation of the catalyst, thus increasing product conversion.
(ii) Increases metal support interaction to minimize the effect of feed contaminants.
(iii) Aids in generating effective surface hydrogen by splitting gas phase hydrogen thus minimizing coke formation on the surface.
(iv) Decelerates the catalyst growth during calcination phase of the catalyst synthesis to maximize the mesopores required for high product selectivity.
The following examples are provided to better illustrate the claimed invention and are not to be interpreted in any way as limiting the scope of the invention. All specific materials, and methods described below, fall within the scope of the invention. These specific compositions, materials, and methods are not intended to limit the invention, but merely to illustrate specific embodiments falling within the scope of the invention. One skilled in the art may develop equivalent materials, and methods without the exercise of inventive capacity and without departing from the scope of the invention. It is the intention of the inventors that such variations are included within the scope of the invention.
Examples
Comparative Example 1 : Catalyst A
Catalyst A was prepared using the well-established sulfated alumina zirconia synthesis route as known to those skilled in the art as shown in US Pat No. 6,448,198 B l . The corresponding references for the catalyst design have been provided for reference. Briefly, high surface area Zirconium hydroxide (Zr(OH)4) and pseudo-boehmite were co-mulled together to form an intimate mixture. They were then extruded into 1mm diameter and 2mm length extrudes. The extrudes were then exposed to 1 M sulfuric acid (15 ml/gm of extrudes) and subsequently vacuum filtered to remove the excess sulfate ions. The extrudes were then calcined at 600°C for 3 hours to form crystalline sulfated alumina zirconia catalyst. The catalyst had 0.24 ml/g pore volume at the end of the calcination. Platinum with 0.3 wt% was then incoiporated into the catalyst by wet impregnation technique as known to those skilled in the art. This catalyst was designated catalyst A.
7 gm of catalyst A was loaded in a fixed bed reactor where it was calcined in air at 500°C for 2 hours and subsequently reduced in Hydrogen for 1 hour. A reaction mixture containing the following composition was then flown on the catalyst at 30 bar and 135°C for 200 hours. The result of the product sample drawn at 50 and 200 hours respectively is shown in Table 1.
Table 1 : Feed composition for fixed bed reactor testing of the catalyst compositions for activity towards hydrocarbon isomerization
Catalyst B was prepared using the popular metal doped sulfated zirconia catalyst synthesis route as known to those skilled in the art and also described in the patent, EP0532153B1. Briefly, high surface area zirconium hydroxide was prepared by rapidly mixing zirconium carbonate and ammonia solutions. After washing and sieving to desired size, Iron (Fe) and Manganese (Mn) nitrate solutions were added to the support material via incipient wetness impregnation method. The catalyst was subsequently dried and calcined at 725°C for one hour. 0.3% Platinum was incorporated into the catalyst via incipient wetness impregnation method. The testing procedure described in example 1 was used to evaluate catalyst B's performance. The results of which are detailed in Table 2.
Example 3: Catalyst Z
Base catalyst was synthesized using the method described in the open literature (reference provided in the previous sections). Briefly, high surface zirconium hydroxide and pseudo boehmite were co-mulled together and impregnated with IN H2S0 by using 15ml/gm- of the support material. Excess acid was drained and the sulfated
support was dried at 120°C for several hours. Gallium was then introduced into the support by adding its corresponding nitrate salt to achieve 3% loading by incipient wetness technique. The mixture was then dried and is labeled Catalyst Z. Additive Composition 1 - Catalyst Zl
Additive for catalyst Zl was first prepared by mixing nitrate salts of Strontium, Cerium, Samarium and Manganese. 25.5 gms of Mn(N03)2 50% solution, 5 gms of Sr(N03)2, 9.3 gms of Ce(N03)3.6H20 1.1 gms of Sm(N03)3.6H20 were mixed together in desired amount of water. 13.4 gms of 35% H202 was added to the mixture while stirring. 2.4 gms of Oxalic acid was then added to the mixture. Finally 1 gm of Pluronic (F127) and 1 gm of PEG were added to final mixture and stirred for 1 hour. The pH of the final solution was brought to 10.5 using TMAOH. The product was filtered, washed and calcined at 500°C. The XRD profile of the product is shown in figure 1. The molecular formula of the additive Zl thus formed is SrCe0.9Sm0.iMn3Om where m is defined to render the overall charge neutral.
The additive thus produced is added to catalyst Z shown in example 1 and extruded into lmm diameter and 2mm length extrudes. The final catalyst formulation was calcined at 700°C for 3 hours. 0.3 wt% Platinum was added to the calcined extrudes by incipient wetness impregnation method. The catalyst is labeled Zl and the isomerization test results with the feed shown in comparative example 1 are shown in Table 2.
Additive Composition 2 - Catalyst Z2
Additive for catalyst Z2 was first prepared by mixing nitrate salts of Strontium, Cerium, Ytterbium and Manganese. 25.5 gms of Mn(N03)2 50% solution, 5 gms of Sr(N03)2, 9.3 gms of Ce(N03)3.6H20 1.1 gms of Yb(N03)3.6¾0 were mixed together in desired amount of water. 13.4 gms of 35% H202 was added to the mixture while stirring. 2.4 gms of Oxalic acid was then added to the mixture. Finally 1 gm of Pluronic (F127) and 1 gm of PEG were added to final mixture and stirred for 1 hour. The pH of the final solution was brought to 10.5 using TMAOH. The product was filtered, washed and calcined at 500°C. The XRD profile of the product is shown in figure 2. The
molecular formula of the additive Z2 thus formed is SrCe0-.9Ybo.iMn5Om where m is defined to render the overall charge neutral.
The additive thus produced is added to catalyst Z shown in example 1 and extruded into 1mm diameter and 2mm length extrudes. The final catalyst formulation was calcined at 700°C for 3 hours. 0.3 wt% Platinum was added to the calcined extrudes by incipient wetness impregnation method. The catalyst is labeled Z2 and the isomerization test results with the feed shown in comparative example 1 is shown in Table 2. Additive Composition 3 - Catalyst Z3
Additive for catalyst Z3 was first prepared by mixing nitrate salts of Strontium, Cerium, Ytterbium and Ruthenium. 17 gms of Ru(N03)2, 5 gms of Sr(N03)2, 9.3 gms of Ce(N03)3.6H20 1.1 gms of Yb(N03)3.6H20 were mixed together in desired amount of water. 13.4 gms of 35% H202 was added to the mixture while stirring. 2.4 gms of Oxalic acid was then added to the mixture. Finally 1 gm of Pluronic (F127) and 1 gm of PEG were added to final mixture and stirred for 1 hour. The pH of the final solution was brought to 10.5 using TMAOH. The product was filtered, washed and calcined at 500°C. The XRD profile of the product is shown in figure 2. The molecular formula of additive thus formed is
where m is defined to render the overall charge neutral.
The additive thus produced is added to catalyst Z shown in example 1 and extruded into lmm diameter and 2mm length extrudes. The final catalyst formulation was calcined at 700°C for 3 hours. 0.3 wt% Platinum was added to the calcined extrudes by incipient wetness impregnation method. The catalyst is labeled Z2 and the isomerization test result with the feed shown in comparative example 1 is shown in
Table.2.
Table 2: Performance results for the catalysts (Zl , Z2 and Z3) prepared as per the invention in comparison to those known to prior art (A and B) shown in comparative examples -
2,2 -DMB 2,2-DMB
Temperature Pressure of n-Hex n-Hex
Catalyst 20 hour 200 hour of reaction reaction
operation operation
A 135°C 30 bar 23% 12.0%
B 135°C 30 bar 24% 1 1.4%
Zl 135°C 30 bar 34.5% 34.4%
Z2 135°C 30 bar 33% 34.2%
Z3 135°C 30 bar 31 % 30.5%
The catalysts prepared with the invention described herein, namely catalysts Zl , Z2 and Z3 exhibit excellent performance characteristics in terms of product conversion, low temperature operation and high tolerance to feed contaminants.
Claims
1. An additive composition comprising mixed metal oxide having the general formula:
AxByC(,.y)DzOm
wherein:
A is one or more metal elements selected from the group consisting of Group IIA of the periodic table;
B, C is one or more metal elements selected from the lanthanide group series of the periodic table or Yttrium;
D is one or more metal elements selected from the group consisting of Manganese, Cobalt, Copper, Nickel or Ruthenium;
x is a number defined by 0.5 < x < 4
y is a number defined by 0<=y<=l
z is a number defined by 2 < z < 6
m is a number which renders the catalyst substantially neutral.
2. The additive composition as claimed in claim 1 , wherein A is selected from the group consisting of Strontium, Magnesium, Barium or mixtures thereof.
3. The additive composition as claimed in claim 1 , wherein B and C are selected from the group consisting of Cerium, Samarium, Ytterbium, Lanthanum, Neodymium, Yttrium or mixtures thereof.
4. The additive composition as claimed in claim 1 , wherein A is Strontium, B is Cerium or Yttrium, C is Samarium or Ytterbium and D is Manganese or Ruthenium.
5. The additive composition as claimed in claim 1 , wherein the mole percent of element A is in the range of 0.1 < A < 0.25; mole percent of elements B, C are in the range of 0.05 < B, C < 0.2; mole percent of element D is in the range of 0.1 < D < 0.35; and the valence charge of oxygen is such that the overall charge of the molecule is neutral.
6. A process for preparing the additive composition as claimed in claim 1 comprising:
a. dissolving water soluble salts of A, B, C and D to obtain the general formula as claimed in claim 1 ;
b. adding a precipitating agent to the resultant mixture of step (a); c. adjusting the pH of the solution of step (b) to about 9 - 12;
d. filtering and washing the resulting precipitant of step (c);
e. calcining the precipitant of step (d) at 300°C to 600°C for 1 hour to 6 hours to obtain the additive composition.
7. The process as claimed in claim 6, wherein the salts of A, B, C and D are selected from the group consisting of nitrate, acetate, chloride or sulfate.
8. The process as claimed in claim 6, wherein the process optionally comprises adding an oxidizing agent or a surfactant to the mixture of step (a).
9. The process as claimed in claim 8, wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, chlorate, perchlorate, hypochlorite, nitric acid, sulfuric acid, potassium permanganate or mixtures thereof.
10. The process as claimed in claim 8, wherein the oxidizing agent is added in an amount of 100% in excess of the moles of element D in the additive composition.
1 1. The process as claimed in claim 8, wherein the surfactant is selected from the group consisting of polyvinyl alcohol (PVA), Triton X-100, Pluronic F127, Polyethylene glycol (PEG), sodium salt of polyacrylic acid (Na-PAA) or mixtures thereof.
12. The process as claimed in claim 8, wherein the surfactant is added in an amount of 50% in excess of moles of element A present in the additive composition.
13. The process as claimed in claim 6, wherein the precipitating agent is selected from the group consisting of sodium hydroxide, sodium carbonate, oxalic acid, sodium oxalate, ammonium oxalate or mixtures thereof.
14. The process as claimed in claim 6, wherein the precipitating agent is added in an amount so as to obtain a final pH value of at least 9.
15. The process as claimed in claim 6, wherein the pH of solution of step (b) is adjusted using tetramethylammonium hydroxide (TMAOH).
16. The process as claimed in claim 6, wherein the precipitant of step (d) is calcined at 500°C for 4 hours.
17. A mixed metal oxide catalyst comprising the additive composition as claimed in any of the preceding claims.
18. The mixed metal oxide catalyst as claimed in claim 17, wherein said mixed metal oxide catalyst is selected from the group consisting of Group III and Group IV of the periodic table.
19. The mixed metal oxide catalyst as claimed in claim 1 8, wherein said mixed metal oxide catalyst is selected from the group consisting of a sulfated or a tungsated metal oxide of Zirconium or Aluminum or mixtures thereof.
20. The mixed metal oxide catalyst as claimed in claim 17, wherein said mixed metal oxide catalyst optionally consists of a hydrogenating metal selected from the, group consisting of Manganese, Iron, Gallium, Copper, Cobalt or mixtures thereof.
21. The mixed metal oxide catalyst as claimed in claim 17, wherein the additive composition is added to the mixed metal oxide catalyst prior to calcination.
22. The mixed metal oxide catalyst as claimed in claim 17, wherein about 0.5 to 25 weight percent of the additive composition is added to the mixed metal oxide catalyst.
23. The mixed metal oxide catalyst as claimed in claim 17, wherein said mixed metal oxide catalyst further comprises a Group VIII metal selected from the group consisting of Platinum, Palladium, Rhenium, Rhodium, Iridium, Ruthenium, Gold or mixtures thereof.
24. The mixed metal oxide catalyst as claimed in claim 23, wherein about 0.1 % to 5% of Group VIII metal is present in the mixed metal oxide catalyst.
25. The mixed phase catalyst as claimed in claim 17, wherein the additive composition has a fluorite phase and/or a spinel phase and/ or a mullite phase when characterized with Transmission Electron Microscopy (TEM) or Scanning Transmission Electron Microscopy (STEM)/ Energy-disperisve X-ray Analyser (EDX) techniques.
26. A process for converting hydrocarbons by contacting a feed with the mixed metal oxide catalyst as claimed in claim 17.
27. The process for converting hydrocarbons as claimed in claim 26,· wherein the hydrocarbon conversion process is selected from the group consisting of cracking, hydrocracking, aromatic alkylation, isoparaffin alkylation, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation or dealkylation.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16792316.8A EP3294451A4 (en) | 2015-05-08 | 2016-03-04 | Additive composition for mixed metal oxide catalysts and its use in hydrocarbon conversion processes |
| US15/572,507 US20180133695A1 (en) | 2015-05-08 | 2016-03-04 | Additive composition for mixed metal oxide catalysts and its use in hydrocarbon conversion processes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN1840/MUM/2015 | 2015-05-08 | ||
| IN1840MU2015 | 2015-05-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016181407A1 true WO2016181407A1 (en) | 2016-11-17 |
Family
ID=57249007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IN2016/000061 WO2016181407A1 (en) | 2015-05-08 | 2016-03-04 | Additive composition for mixed metal oxide catalysts and its use in hydrocarbon conversion processes |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20180133695A1 (en) |
| EP (1) | EP3294451A4 (en) |
| WO (1) | WO2016181407A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109364943A (en) * | 2018-12-12 | 2019-02-22 | 辽宁大学 | A kind of efficient cryogenic denitrating catalyst and its preparation method and application |
| CN110038619A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of production method of hydrocracking catalyst |
| CN110038623A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN115041161A (en) * | 2022-07-26 | 2022-09-13 | 青岛理工大学 | Manganese-loaded biochar catalyst and preparation method and application thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3032599A (en) | 1958-05-05 | 1962-05-01 | Phillips Petroleum Co | Sulfate-treated zirconia-gel catalyst |
| US3132110A (en) | 1959-01-12 | 1964-05-05 | Union Oil Co | Coprecipitated alumina-zirconium oxide sulfate-containing catalyst |
| EP0532153A2 (en) | 1991-06-03 | 1993-03-17 | SUN COMPANY, INC. (R&M) | Isomerisation of hydrocarbons with solid superacid catalyst at supercritical or near critical conditions |
| EP1002579A1 (en) | 1998-11-13 | 2000-05-24 | Uop | Sulfated layered catalyst for use in a paraffin isomerization process |
| US6080904A (en) | 1993-07-22 | 2000-06-27 | Mobil Oil Corporation | Isomerization process |
| US6107235A (en) | 1996-09-05 | 2000-08-22 | Japan Energy Corporation | Solid acid catalyst and process for preparing the same |
| US6448198B1 (en) | 1997-10-13 | 2002-09-10 | Total Raffinage Distribution S.A. | Acid catalyst with a sulfated zirconia base and its uses |
| RU2191627C2 (en) | 1995-11-30 | 2002-10-27 | Акцо Нобель Н.В. | Method of producing catalyst suitable for use in isomerization of hydrocarbons, catalyst produced by said method and its application |
| US20050161368A1 (en) | 2001-08-29 | 2005-07-28 | Gillespie Ralph D. | High-activity isomerization catalyst and process |
| US7015175B2 (en) | 2001-08-29 | 2006-03-21 | Uop Llc | High-activity isomerization catalyst and process |
| EP1914216A1 (en) * | 2006-06-19 | 2008-04-23 | Otkrytoe Aktsionernoe Obschestvo "Nauchno- Proizvodstvennoe Predpriyatie Neftekhim" | Method for isomerising light gasoline fractions |
| EP2100663B1 (en) * | 2008-03-14 | 2012-05-02 | Dia-Nitrix Co., Ltd. | Catalyst for synthesizing acrylonitrile and process for producing acrylonitrile |
| US20140219878A1 (en) | 2011-09-23 | 2014-08-07 | Shubin, Inc. | Mixed phase oxide catalysts |
| US9040762B2 (en) | 2011-05-24 | 2015-05-26 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
-
2016
- 2016-03-04 US US15/572,507 patent/US20180133695A1/en not_active Abandoned
- 2016-03-04 WO PCT/IN2016/000061 patent/WO2016181407A1/en active Application Filing
- 2016-03-04 EP EP16792316.8A patent/EP3294451A4/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3032599A (en) | 1958-05-05 | 1962-05-01 | Phillips Petroleum Co | Sulfate-treated zirconia-gel catalyst |
| US3132110A (en) | 1959-01-12 | 1964-05-05 | Union Oil Co | Coprecipitated alumina-zirconium oxide sulfate-containing catalyst |
| EP0532153A2 (en) | 1991-06-03 | 1993-03-17 | SUN COMPANY, INC. (R&M) | Isomerisation of hydrocarbons with solid superacid catalyst at supercritical or near critical conditions |
| US6080904A (en) | 1993-07-22 | 2000-06-27 | Mobil Oil Corporation | Isomerization process |
| RU2191627C2 (en) | 1995-11-30 | 2002-10-27 | Акцо Нобель Н.В. | Method of producing catalyst suitable for use in isomerization of hydrocarbons, catalyst produced by said method and its application |
| US6107235A (en) | 1996-09-05 | 2000-08-22 | Japan Energy Corporation | Solid acid catalyst and process for preparing the same |
| US6448198B1 (en) | 1997-10-13 | 2002-09-10 | Total Raffinage Distribution S.A. | Acid catalyst with a sulfated zirconia base and its uses |
| EP1002579A1 (en) | 1998-11-13 | 2000-05-24 | Uop | Sulfated layered catalyst for use in a paraffin isomerization process |
| US20050161368A1 (en) | 2001-08-29 | 2005-07-28 | Gillespie Ralph D. | High-activity isomerization catalyst and process |
| US7015175B2 (en) | 2001-08-29 | 2006-03-21 | Uop Llc | High-activity isomerization catalyst and process |
| EP1914216A1 (en) * | 2006-06-19 | 2008-04-23 | Otkrytoe Aktsionernoe Obschestvo "Nauchno- Proizvodstvennoe Predpriyatie Neftekhim" | Method for isomerising light gasoline fractions |
| EP2100663B1 (en) * | 2008-03-14 | 2012-05-02 | Dia-Nitrix Co., Ltd. | Catalyst for synthesizing acrylonitrile and process for producing acrylonitrile |
| US9040762B2 (en) | 2011-05-24 | 2015-05-26 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
| US20140219878A1 (en) | 2011-09-23 | 2014-08-07 | Shubin, Inc. | Mixed phase oxide catalysts |
Non-Patent Citations (5)
| Title |
|---|
| "Catalytic performance of Re/Ga 0 /WO /Zr0 catalyst for n-Hexane isomerization", CHI.J. OF. CATAL., vol. 30, no. 9, September 2009 (2009-09-01), pages 859 - 863 |
| "Effect of isopropanol aging of Zr(OH) on n-hexane isomerization over Pt-S0 -/Al203-Zr02", CATALYSIS TODAY, vol. 148, no. 1-2, October 2009 (2009-10-01), pages 70 - 74 |
| "Effect of isopropanol aging of Zr(OH) on n-hexane isomerization over Pt-S0 -1 Ah03-Zr02", CATALYSIS TODAY, vol. 148, no. 1-2, October 2009 (2009-10-01), pages 70 - 74 |
| HINO ET AL.: "Synthesis of Solid superacid catalyst with acid strength of HO < -16.04", J.C.S. CHEM. COMM., vol. 851 - 852, 1980, pages 573 |
| See also references of EP3294451A4 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038619A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of production method of hydrocracking catalyst |
| CN110038623A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN110038619B (en) * | 2018-01-16 | 2021-12-07 | 中国石油化工股份有限公司 | Production method of hydrocracking catalyst |
| CN109364943A (en) * | 2018-12-12 | 2019-02-22 | 辽宁大学 | A kind of efficient cryogenic denitrating catalyst and its preparation method and application |
| CN115041161A (en) * | 2022-07-26 | 2022-09-13 | 青岛理工大学 | Manganese-loaded biochar catalyst and preparation method and application thereof |
| CN115041161B (en) * | 2022-07-26 | 2024-02-23 | 青岛理工大学 | Manganese-loaded biochar catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20180133695A1 (en) | 2018-05-17 |
| EP3294451A4 (en) | 2019-01-02 |
| EP3294451A1 (en) | 2018-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10307737B2 (en) | Transition metal-noble metal complex oxide catalyst for dehydrogenation prepared by one-pot synthesis and use thereof | |
| JP4707800B2 (en) | Hydrocarbon aromatization catalyst composition | |
| KR100928608B1 (en) | Reforming Catalyst of Hydrocarbon and Method of Making the same, and Reforming Method of Hydrocarbon Using the Catalyst | |
| US7989386B2 (en) | Multi-layer catalyst made from niobium for the catalytic conversion of hydrocarbons | |
| US20180133695A1 (en) | Additive composition for mixed metal oxide catalysts and its use in hydrocarbon conversion processes | |
| US11548835B2 (en) | Hybrid catalyst for selective and stable olefin production | |
| CN107051420B (en) | N-butane isomerization catalyst and preparation method thereof | |
| JPH05146679A (en) | Method for producing catalyst or its precursor | |
| US20060060505A1 (en) | Catalyst and process for selective hydrogenation | |
| KR20180079178A (en) | Composite catalyst support, dehydrogenation catalysts and preparation method thereof | |
| US7550637B2 (en) | Catalyst and process for selective hydrogenation | |
| WO2017003319A1 (en) | Catalyst for isomerisation of paraffin hydrocarbons and method of preparation thereof | |
| JP2013521221A (en) | Conversion of sugars, sugar alcohols, or glycerol into valuable chemicals using active zirconium oxide supported catalysts | |
| RU2741547C2 (en) | Obtaining a zsm-5 based catalyst; use in process of ethylbenzene dealkylation | |
| US20080064908A1 (en) | Catalyst For Cycloolefin Production And Process For Production | |
| KR20220103803A (en) | Catalyst suitable for hydrocarbon conversion reaction, method for preparing same and use thereof | |
| EP1374993A2 (en) | Solid acid catalyst containing platinum group metal component and method for preparation thereof | |
| TW201714668A (en) | Multi-metallic catalyst doped with phosphorus and a lanthanide | |
| JP4931099B2 (en) | Catalyst for producing cycloolefin and method for producing cycloolefin | |
| JP7144208B2 (en) | Catalyst for producing cumene and its application | |
| KR100305482B1 (en) | Catalyst for Dehydrogenation with Macropores | |
| JPH0529503B2 (en) | ||
| CN112058255A (en) | Alkane dehydrogenation catalyst and preparation method thereof | |
| US11745169B1 (en) | Single atom metal doped ceria for CO oxidation and HC hydrogenation/oxidation | |
| US11697105B2 (en) | Method for catalyst production for C5-C12 paraffins isomerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16792316 Country of ref document: EP Kind code of ref document: A1 |
|
| DPE2 | Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101) | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 15572507 Country of ref document: US |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2016792316 Country of ref document: EP |